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Advanced CO2/H2 Separation Materials Incorporating Active Functional Agents
Shingo Kazama
Research Institute of Innovative Technology for the Earth (RITE)
GCEP Symposium October 4, 2011 Stanford University, Stanford, California
Outline
1. Membrane Challenge for Cost Reduction in CCS 2. CO2 Molecular Gate Function for CO2 Separation Membrane 3. Dendrimers for Promising Molecular Gate Materials 4. Dendrimer Hybrid Membranes 5. Next Generation of CO2 Molecular Gate in GCEP Research 6. Concluding Remarks
3
Absorption
CO2 Capture Methods for CCS
3. Storage ( CO2 Storage Group in RITE ) Geological Utilization Ocean
2. CO2 Capture (Chemical Research Group in RITE )
1. CO2 Sources
Fossil Fuel Bio-Mass
Gasification Shift
reaction
Blast-furnace Power plant (Combustion)
Adsorption Membrane
Polymer Zeolite Carbon Nono composite material
Zeolite, Mesoporous silica
Plant analysis for the decreasing energy and cost
R. & D.
Absorbent Novel process Waste heat utilization
CO2 > 99% CO2 < 2%
Abs
orbe
r
HEX
absorbent
Reg
ener
ator
CO2 > 95%
CO2 < 2% CO2 > 97%
CO2 < 2%
Present Cost of CCS (coal fired power plant)
recovery amount:1Mt-CO2/yr、 distance:20km、pressure:7MPa injection method:ERD、 injection amount :0.1Mt-CO2/yr/well
Power loss for extraction steam from low pressure turbine: 0.05kWh/MJ
NET storage =670/1000
NET storage =502/1000
New plant
Existing plant
avoided cost JPY/t-CO2
coal fired plant to aquifer
Existing coal fired plant to aquifer
Upgrading desulfurization facilities &
Auxiliary coal fired boiler
Separation Pressurization Transportation Injection income
Capture cost 4,200JPY/t-CO2
CCS total cost 7,300JPY/t-CO2
Membrane Performance and CO2 Capture Cost
IGCC with WGS (CO2 conc. 40%): CO2 Permeance 7.5 x 10-10 m3/(m2 s Pa) CO2/H2 Selectivity 30: Cost:1,500JPY/t-CO2 CO2/H2 Selectivity 100: Cost:1,000JPY/t-CO2
Ref: MDEA: 2,500-3,00JPY/t-CO2
Natural Gas (CO2 conc. 50%): CO2 Permeance 7.5 x 10-10 m3/(m2 s Pa) CO2/CH4 Selectivity 40: Cost:<1,000JPY/t-CO2 1/5 of MDEA method
Basic Membrane Performance: Permeance & Selectivity
Sleipner Project@ Statoil from HP
EAGLE@J-POWER from HP
What ideal membrane ?
Dry Towel Wet Towel
Air Air
Textile
Water Fiber
A wet towel balloon may hint an ideal gas separation membrane.
CO2 :0.33nm H2 :0.29 nm Feed
Permeate
Pressure Difference
High
Low
Basic Concept of CO2 Molecular Gate for CO2/H2 Separation
Excellent CO2 selectivity
Membrane Material
Polyamidoamine (PAMAM) dendrimer (0-OH-PAMAM dendrimer)
H2 Blockage by CO2 in Dendrimer
H2Permeability Pure gas > Mixed-gas (CO2: 5 %)
CO2 blocks H2 permeation
Mixed-gas (CO2/H2)
Pure H2
10 -18
10 -17
10 -16
10 -15
0 20 40 60 80 100
H 2 P
erm
eabi
lity
[Nm
3 m m
-2 s -1
Pa -1
]
RH [%] in Feed Gas
Mixed-gas (H2/CO2=95%/5%)
Pure H2
4-OH PAMAM dendrimer
CO2 H2
CO2
Carbamate Formation
Pseudo-cross-linkage
H2 permeation blockage
Possible Model of H2 Permeation Blockage
Carbamate (mol/mol-dendrimer)
2.6
Bi-carbonate (mol/mol-dendrimer)
0.36
Concentration of Carbamate & Bi-carbonate in 4-OH Dendrimer at 80 RH%
TMPTMA
PEGDMA
+
+
O-OH-PAMAM dendrimer
Dendrimer Hybrid Membrane for CO2 Capture from Pressurized Gas Stream
UV Curing
PAMAM/PEGDMA/TMPTMA = 50/37.5/12.5, Feed : 100 mL/min, Sweep: 20 ml/min, T = 313 K, R.H. = 80%
CO2/H2 Separation Properties of Dendrimer Hybrid Membrane at Elevated Pressure
10 -14
10 -13
10 -12
10 -11
10 -10
1
10
100
1000
0 1 2 3 4 5 6 7
CO 2
H 2
α
Perm
eanc
e (Q)/ (
m 3 (
STP)
/(m2 s
Pa)) C
O2 /H
2 Selectivity
PCO2, atm
α(C
O2 /H
2 )/(‐)
CO2 Partial pressure
H2
CO2
α
CO2 Permeance / m3(STP)/(m2 s Pa)
CO2/H2 Separation Properties of Various Dendrimer Hybrid Membranes
(1) H. Lin, B.Freeman et al., Science, 311, 639-642 (2006)
Film Thickness: 500 µm
CO
2/H2 S
elec
tivity
(-)
1 2 3
4 5
6
7
8
9
10 11
12
0
10
20
30
40
50
10 -14 10 -13 10 -12 10 -11 10 -10 10 -9
(1)
RITE
Science
★
CO2 partial press.: 6 bar Temperature: 313 K
Target value for 1,500JPY/t-CO2 CO2 permeance: 7.5 x 10-10 m3/(m2 s Pa) CO2/H2 Selectivity: 30
Development of Membrane Module
Dendrimer/ Polymeric matrix : Dendrimer Hybrid
Now fabricating dendrimer membrane modules with membrane module makers under METI funding
14
CO2/CH4Separation Properties of Dendrimer Hybrid Membrane
Gas
per
mea
nce
/ Nm
3 /(m
2 s P
a)
CO2 Partial Pressure / kPa
CO2/CH4 Selectivity: 58
QCO2 QCH4
CH4
CO2
GCEP Challenge in Molecular Gate Membrane
Present Situation: High CO2/H2 selectivity at large CO2 partial pressure at high water vapor content, e.g. 80 RH% or more - weak point for dry condition !
GCEP Challenge: - Higher Permeance and Selectivity - Well working at lower water vapor
CO2
H2O HCO3
-
HCO3-
HCO3-
2 R-NH2
Hopping CO2
CO2
Gas Feed
Permeate
R-NH2 Sorption
Desorption
Diffusion
CO2 Transportation Model of Current Dendrimer Hybrid Membrane
CO2 H2O
CO2 H2O
Hopping CO2
Sc-CO2 Structure Directing Method for Next Generation Membrane
-R-N-C-O・・・N-R- N O
N
N - +
N
Inject Sc-CO2
Remove Sc-CO2
Amino moiety
CO2
Pre-formed Solid Membrane
carbamate formation
CO2 Hopping Channel
Basic Concept:
Syringe pump Back-pressure
regulator High-pressure view cell
Sapphire window
Pre-formed membrane
Camera
Pressure:10 MPa Temperature:20-60℃
CO2 Membrane under Sc-CO2
Diagram of Set-up for Sc-CO2 Structure Directing Method
Poly(amidoamine) dendrimer
Polyethylene glycol dimethacrylate
Third Component
QCO2 Permeance m3/(m2 s Pa) 4.4x10-12 CO2/H2 Selectivity 140
8.5x10-12 210
Post-: Pre-:
SC-CO2 treatment condition: 10 MPa, 4 hr, 333 K
CO2/H2 separation performance
Pre-treated Membrane
Effect of Sc-CO2 Treatment (1)
20
0
5
10
15
20
25
30
1.00E-13
1.00E-12
1.00E-11
0 1 2 3 4 5
QCO2
QHe
α
α C
O2/H
e
Gas Perm. Test(DPCO2= 100 kPa, 90%RH, 40oC)
Q (m
3 (ST
P)/(m
2 s P
a))
sc-CO2 treatment time (h)
Poly ethylene imine (PEI)
sc-CO2 treatment: Temp. 50 oC,Press. 10 MPa
Effect of Sc-CO2 Treatment (2)
CO
2/He
Sele
ctiv
ity
- Membrane application for CO2 capture from a pressurized gas stream, e.g. IGCC, Natural gas, is promising way of reducing CO2 capture cost and energy. - Molecular Gate Membrane (MGM) is proposed for high CO2 selectivity over H2. - Dendrimer membrane has good CO2 separation performance over a wide range of CO2 partial pressure and at highly water vapor condition. - Next generation MGMs that work well in a wide range of humidity in a feed gas and have excellent selectivity and permeance are now under development in GCEP project.
Concluding Remarks
Researchers: Dr. Yuichi Fujioka, Dr. Katsunori Yogo Dr. Shuhong Duan, Dr. Teruhiko Kai, Dr. Kazuya Goto, Dr. Ryo Nagumo, Dr. Ryosuke Shimizu, Dr. Hiroshi Machida Dr. Ikuo Taniguchi, Dr. Kouta Yamazaki
Student of NAIST (Nara Institute of Science and Technology) : Mr. Tomoyuki Kato, Mr. Akihito Itoyama
This study is supported by -GCEP, Stanford University -Ministry of Economy, Trade and Industry (METI), Japan. -Nippon Steel Engineering Co., Ltd.
Acknowledgements
November 2012 - Kyoto will welcome experts in greenhouse gas control technologies from across the world!
1. Dates : Sun. 18th – Thur. 22nd November, 2012 2. Venue : Kyoto International Conference Center, Japan
3. Organizers : RITE & IEAGHG 4. Call for Papers open: Sep.26th, 2011 / Abstract Submission Deadline: Feb.10th, 2012 Themes are: Capture; Geo Storage; Other Storage; Industrial sources; Transport; Negative CO2; CO2 utilisation options; Demonstration; Tech Assess & Integration; Commercial Issues; Public Perception; Policies; Legal & Regulatory; Education, training, and capacity building
5. On-line Conference Registration Early Bird open: April 23rd, 2012 / Late on-line registration: July 24th – November 17th, 2012
6. Programme Overview ( Subject to change)
7. Website http://www.ghgt.info/ !!! Sponsors are now being sought !!!
GHGT-11
- 11th International Conference on Greenhouse Gas Control Technologies -
GHGT-10 Plenary session
GHGT-10 : Poster session
24
Research Institute of
Innovative Technology for the Earth
Contact: kazama@rite. or. jp
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